Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/002—Priming paints
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09D133/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/022—Emulsions, e.g. oil in water
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

• the present technology relates to a water-based primer composition for a sealant.
• a primer In general, to adhere a sealant for construction to an adherend formed from an inorganic hard material, such as mortar, a primer needs to be applied to the adherend.
• Japan Unexamined Patent Publication No. 2014-172992 as a water-based primer composition.
• Japan Unexamined Patent Publication No. 2014-172992 describes a water-based primer composition, containing an acrylic emulsion, for a sealant, the water-based primer composition being an acrylic emulsion containing acrylic particles;
• an average particle diameter of the acrylic particles being 0.6 ⁇ m or less
• the acrylic particles being particles of polymer obtained by subjecting a polymerizable monomer (A) containing a (meth)acryloyl group in the presence of a persulfate (B) which is a polymerization initiator;
• polymerizable monomer (A) containing a (meth)acrylic acid alkyl ester monomer (A1) and a hydroxy group-containing polymerizable monomer
• a molar ratio (OH/A1) of the hydroxy group (OH) contained in the hydroxy group-containing polymerizable monomer (A2) to the (meth)acrylic acid alkyl ester monomer (A1) being 0.05 or greater;
• the inventors of the present technology prepared and evaluated a primer composition by using Japan Unexamined Patent Publication No. 2014-172992 as a reference, and found that there are some cases where such a primer composition may have poor water resistance.
• the present technology provides a water-based primer composition for a sealant, the water-based primer composition having excellent water resistance.
• a predetermined effect can be achieved by a water-based primer composition for a sealant, the water-based primer composition containing a (meth)acrylic emulsion containing a (meth)acrylic particle and a tertiary amine (B),
• the (meth)acrylic particle being a particle of a polymer obtained by polymerizing a polymerizable monomer (A) having a (meth)acryloyl group;
• the polymerizable monomer (A) containing an epoxy group-containing polymerizable monomer (A1) having an epoxy group, a (meth)acrylic silane coupling agent (A2), a (meth)acrylic acid alkyl ester monomer (A3), a (meth)acrylic acid monomer (A4), and a hydroxy group-containing polymerizable monomer (A5) having a hydroxy group, or
• the polymerizable monomer (A) containing a phosphoric acid group-containing polymerizable monomer (AP) having a phosphoric acid group, a (meth)acrylic acid alkyl ester monomer (A6), a (meth)acrylic acid monomer (A7), and a hydroxy group-containing polymerizable monomer (A8) having a hydroxy group, and
• a content of the (meth)acrylic particle being from 15 to 60 mass %.
• the present technology provides the following features.
• a water-based primer composition for a sealant containing a (meth)acrylic emulsion containing a (meth)acrylic particle and a tertiary amine (B),
• the (meth)acrylic particle being a particle of a polymer obtained by polymerizing a polymerizable monomer (A) having a (meth)acryloyl group;
• the polymerizable monomer (A) containing an epoxy group-containing polymerizable monomer (A1) having an epoxy group, a (meth)acrylic silane coupling agent (A2), a (meth)acrylic acid alkyl ester monomer (A3), a (meth)acrylic acid monomer (A4), and a hydroxy group-containing polymerizable monomer (A5) having a hydroxy group, and
• a content of the (meth)acrylic particle being from 15 to 60 mass %.
• a water-based primer composition for a sealant the water-based primer composition containing a (meth)acrylic emulsion containing a (meth)acrylic particle and a tertiary amine (B),
• the (meth)acrylic particle being a particle of a polymer obtained by polymerizing a polymerizable monomer (A) having a (meth)acryloyl group;
• the polymerizable monomer (A) containing a phosphoric acid group-containing polymerizable monomer (AP) having a phosphoric acid group, a (meth)acrylic acid alkyl ester monomer (A6), a (meth)acrylic acid monomer (A7), and a hydroxy group-containing polymerizable monomer (A8) having a hydroxy group; and
• a content of the (meth)acrylic particle being from 15 to 60 mass %.
• the water-based primer composition for a sealant of an embodiment of the present technology has excellent water resistance.
• (meth)acrylate represents acrylate or methacrylate
• (meth)acryloyl represents acryloyl or methacryloyl
• (meth)acryl represents acryl or methacryl.
• the content of the component means the total content of the two or more types of substances.
• the epoxy group-containing polymerizable monomer (A1) may be referred to as a monomer (A1), (A1), or A1.
• the epoxy group-containing polymerizable monomer (A1) the same applies to the (meth)acrylic silane coupling agent (A2), the (meth)acrylic acid alkyl ester monomer (A3), the (meth)acrylic acid monomer (A4), the hydroxy group-containing polymerizable monomer (A5), the phosphoric acid group-containing polymerizable monomer (AP), the (meth)acrylic acid alkyl ester monomer (A6), the (meth)acrylic acid monomer (A7), and the hydroxy group-containing polymerizable monomer (A8).
• the polymerizable monomer (A) when the polymerizable monomer (A) contains (A1) to (A5), the polymerizable monomer (A) may be referred to as “first monomer composition”, and when the polymerizable monomer (A) contains (AP) and (A6) to (A8), the polymerizable monomer (A) may be referred to as “second monomer composition”.
• the water-based primer composition for a sealant of an embodiment of the present technology (the composition of an embodiment of the present technology) is
• a water-based primer composition for a sealant containing a (meth)acrylic emulsion containing a (meth)acrylic particle and a tertiary amine (B),
• the (meth)acrylic particle being a particle of a polymer obtained by polymerizing a polymerizable monomer (A) having a (meth)acryloyl group;
• the polymerizable monomer (A) containing an epoxy group-containing polymerizable monomer (A1) having an epoxy group, a (meth)acrylic silane coupling agent (A2), a (meth)acrylic acid alkyl ester monomer (A3), a (meth)acrylic acid monomer (A4), and a hydroxy group-containing polymerizable monomer (A5) having a hydroxy group, or
• the polymerizable monomer (A) containing a phosphoric acid group-containing polymerizable monomer (AP) having a phosphoric acid group, a (meth)acrylic acid alkyl ester monomer (A6), a (meth)acrylic acid monomer (A7), and a hydroxy group-containing polymerizable monomer (A8) having a hydroxy group; and
• a content of the (meth)acrylic particle being from 15 to 60 mass %.
• composition according to an embodiment of the present technology is thought to achieve desired effects as a result of having such a configuration. Although the reason is not clear, it is assumed to be as follows.
• the polymerizable monomer (A) is a first monomer composition in the composition of an embodiment of the present technology and such a composition is used as a primer
• the epoxy group contained in a (meth)acrylic particle is subjected to ring opening by a tertiary amine (B) to produce a hydroxy group, and the interaction between the hydroxy group and at least a sealant suppresses infiltration of water and achieves excellent water resistance.
• the base material to which the sealant is applied is an inorganic material, such as mortar
• the hydroxy group can interact with the inorganic material, and excellent water resistance is achieved.
• the polymer main chain is crosslinked because, in the polymer constituting the (meth)acrylic particle, the polymer has epoxy groups, and some of the epoxy groups are ring-opened and bonded each other due to the catalytic effect of the tertiary amine (B). Therefore, excellent water resistance of the primer membrane formed after drying of emulsion is achieved compared to the case of a composition containing a low molecular weight compound having an epoxy group or the like.
• the polymerizable monomer (A) is a second monomer composition in the composition of an embodiment of the present technology, such a composition has excellent adhesion and water resistance.
• composition more easily infiltrates into the adherend, such as mortar, and/or because the phosphoric acid group and an adherend can interact each other because the average particle size of the (meth)acrylic particle contained in the composition is decreased due to the phosphoric acid group contained in the (meth)acrylic particle.
• the (meth)acrylic emulsion contained in the composition of an embodiment of the present technology contains a (meth)acrylic particle as a dispersoid and a dispersion medium such as water, and the (meth)acrylic particle is dispersed (suspended) in the dispersion medium.
• the phase of the (meth)acrylic particle as the dispersoid may be a liquid phase or a solid phase.
• emulsion a system in which a liquid phase dispersoid is dispersed in a liquid phase dispersion medium
• a system in which a solid phase dispersoid is dispersed in a liquid phase dispersion medium is called a “suspension”.
• emulsion includes “suspension”.
• the dispersion medium contains at least water.
• the dispersion medium may further contain an aqueous organic solvent such as alcohols, besides the water.
• An example of a preferable aspect is one in which the dispersion medium is distilled water.
• the content of the (meth)acrylic particle is from 15 to 60 mass % relative to the total amount of the composition of the embodiment of the present technology.
• the content of the (meth)acrylic particle is preferably from 20 to 60 mass %, and more preferably from 25 to 60 mass %, relative to the total amount of the composition of an embodiment of the present technology from the perspective of achieving superior effect of the present technology and excellent adhesion and drying characteristics.
• the content of the (meth)acrylic particle is influenced as is by the used amount of the polymerizable monomer (A) used in the production of the (meth)acrylic emulsion.
• the (meth)acrylic particle may contain an unreacted polymerizable monomer (A).
• the content of the (meth)acrylic particle does not include the amount of the polymerization initiator used to produce the (meth)acrylic particle and the amount of the tertiary amine contained in the composition of an embodiment of the present technology.
• (meth)acrylic particle is the solid content of the (meth)acrylic emulsion.
• the (meth)acrylic particle contained in the (meth)acrylic emulsion is a particle of polymer obtained by polymerizing a polymerizable monomer (A) having a (meth)acryloyl group.
• the main chain of the polymer may be any main chain that contains a repeating unit derived from a (meth)acryloyl group.
• the main chain of the polymer is preferably a (meth)acrylic polymer.
• the (meth)acrylic particle (or the polymer constituting the (meth)acrylic particle) contains an epoxy group, a hydrolyzable silyl group (hydrolyzable silyl group may have a silanol group), an alkyl ester, a carboxy group, and a hydroxy group (hereinafter, these are also referred to as “epoxy groups and the like”) or contains a phosphoric acid group, an alkyl ester, a carboxy group, and a hydroxy group (hereinafter, these are also referred to as “phosphoric acid group and the like”).
• the carbonyl group contained in the repeating unit derived from (meth)acryloyl group may be bonded to the epoxy groups and the like or the phosphoric acid and the like directly or through an organic group.
• the carbonyl group may form the carboxy group or the alkyl ester.
• the organic group is not limited. Examples thereof include a hydrocarbon group that may have a heteroatom.
• the hydrocarbon group is not limited. Examples thereof include aliphatic hydrocarbon groups (including straight-chain, branched chain, and cyclic), aromatic hydrocarbon groups, and combinations thereof.
• the hydrocarbon group may have an unsaturated bond.
• the heteroatom is not limited. Examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen.
• the heteroatom may form a functional group by a combination of the heteroatoms, or the heteroatom and a carbon atom and/or a hydrogen atom.
• the heteroatom may be substituted with a carbon atom constituting the hydrocarbon group. Examples of the group that is formed by substituting the oxygen atom with the carbon atom constituting the hydrocarbon group include oxyalkylene groups and poly(oxyalkylene) groups.
• the weight average molecular weight of the (meth)acrylic particle is preferably from 50000 to 400000, and more preferably from 70000 to 300000, from the perspective of superior effect of the present technology, excellent adhesion, wettability to an adherend, low viscosity, and the like.
• weight average molecular weight (Mw) of acrylic particle is a weight average molecular weight represented in terms of polystyrene, which is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
• the average particle size of the (meth)acrylic particle may be, for example, 0.6 ⁇ m or less and, from the perspective of wettability to an adherend, the average particle size is preferably 0.58 ⁇ m or less, and more preferably 0.55 ⁇ m or less.
• the lower limit value of the average particle size of the (meth)acrylic particle is preferably greater than 0.01 ⁇ m, more preferably 0.015 ⁇ m or greater, and even more preferably 0.02 ⁇ m or greater.
• the average particle size of the (meth)acrylic particle is a value measured by using a particle size distribution analyzer (Nanotrac UPA-EX150, available from Nikkiso Co., Ltd.).
• the polymerizable monomer (A) used in the production of the (meth)acrylic emulsion contains an epoxy group-containing polymerizable monomer (A1) having an epoxy group, a (meth)acrylic silane coupling agent (A2), a (meth)acrylic acid alkyl ester monomer (A3), a (meth)acrylic acid monomer (A4), and a hydroxy group-containing polymerizable monomer (A5) having a hydroxy group (first monomer composition).
• the polymerizable monomer (A) used in the production of the (meth)acrylic emulsion contains a phosphoric acid group-containing polymerizable monomer (AP) having a phosphoric acid group, a (meth)acrylic acid alkyl ester monomer (A6), a (meth)acrylic acid monomer (A7), and a hydroxy group-containing polymerizable monomer (A8) having a hydroxy group (second monomer composition).
• composition of an embodiment of the present technology in both cases where the polymerizable monomer (A) is the first monomer composition and where the polymerizable monomer (A) is the second monomer composition, excellent water resistance is achieved, and excellent adhesion is achieved.
• polymerizable monomer (A) is the first monomer composition.
• the epoxy group-containing polymerizable monomer (A1) as the polymerizable monomer (A) is a compound having a (meth)acryloyl group and an epoxy group.
• the (meth)acryloyl group and the epoxy group can be bonded through an organic group.
• the organic group is synonymous with that described above.
• Examples of the epoxy group-containing polymerizable monomer (A1) include a compound represented by Formula (1) below.
• R 11 is a hydrocarbon group that may have a heteroatom
• R 12 is a hydrogen atom or a methyl group.
• the hydrocarbon group that may have a heteroatom is synonymous with that described above (the same applies hereinafter).
• the hydrocarbon group that may have a heteroatom is preferably an alkylene group that may have an ether bond.
• epoxy group-containing polymerizable monomer (A1) examples include glycidyl (meth)acrylate, and 4-hydroxybutyl(meth)acrylate glycidyl ether.
• the epoxy group-containing polymerizable monomer (A1) can be used alone or in combination of two or more types thereof. In the present technology, the same applies to (A2) to (A8) and (AP) that are used as the polymerizable monomer (A).
• the (meth)acrylic silane coupling agent (A2) as the polymerizable monomer (A) is a compound having a (meth)acryloyl group and a hydrolyzable silyl group.
• hydrolyzable group contained in the hydrolyzable silyl group examples include alkoxy groups and phenoxy groups.
• the alkoxy group contained in the alkoxysilyl group is not limited. Examples thereof include a methoxy group and an ethoxy group.
• the number of the hydrolyzable group contained in one hydrolyzable silyl group may be from 1 to 3.
• the group except the hydrolyzable group bonded to the hydrolyzable silyl group is not limited.
• hydrocarbons groups can be used.
• the hydrocarbon group is not limited. Examples thereof include the groups listed above.
• the hydrocarbon group is preferably an alkyl group, such as a methyl group or an ethyl group.
• the number of the (meth)acryloyl group contained in one molecule of the (meth)acrylic silane coupling agent (A2) may be one or the plural number.
• the number of the hydrolyzable silyl group contained in one molecule of the (meth)acrylic silane coupling agent (A2) may be one or a plurality.
• the (meth)acrylic silane coupling agent (A2) the (meth)acryloyl group and the hydrolyzable silyl group can be bonded through an organic group.
• the organic group is synonymous with that described above.
• Examples of the (meth)acrylic silane coupling agent (A2) include ⁇ -(meth)acryloxypropyltrimethoxysilane, ⁇ -(meth)acryloxypropyltriethoxysilane, ⁇ -(meth)acryloxypropyltripropoxysilane, ⁇ -meth)acryloxypropylmethyldimethoxysilane, ⁇ -(meth)acryloxypropylmethyldiethoxysilane, and ⁇ -(meth)acryloxypropylmethyldipropoxysilane.
• ⁇ -methacryloxypropyltriethoxysilane and ⁇ -methacryloxypropylmethyldiethoxysilane are preferable from the perspective of superior effect of the present technology and excellent adhesion and storage stability.
• the (meth)acrylic acid alkyl ester monomer (A3) as the polymerizable monomer (A) may be any alkyl ester of (meth)acrylic acid.
• the alkyl group constituting the alkyl ester is not limited.
• the alkyl group may be a straight-chain, branched, or cyclic alkyl group.
• Examples of the (meth)acrylic acid alkyl ester monomer (A3) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isoamyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, cyclopentyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, cyclooctyl (meth
• Examples of the (meth)acrylic acid monomer (A4) as the polymerizable monomer (A) include (meth)acrylic acid.
• the hydroxy group-containing polymerizable monomer (A5) as the polymerizable monomer (A) may be any compound having a (meth)acryloyl group and a hydroxy group.
• the (meth)acryloyl group and the hydroxy group can be bonded through an organic group.
• the organic group is not limited.
• the organic group is synonymous with that described above.
• Examples of the hydroxy group-containing polymerizable monomer (A5) include a compound represented by Formula (2) below.
• R 21 is a hydrocarbon group that may have a heteroatom
• R 22 is a hydrogen atom or a methyl group.
• the hydrocarbon group that may have a heteroatom is synonymous with that described above.
• the hydrocarbon group that may have a heteroatom is preferably an alkylene group.
• hydroxy group-containing polymerizable monomer (A5) examples include hydroxyethyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate.
• the molar ratio (A1/A3) of the epoxy group-containing polymerizable monomer (A1) to the (meth)acrylic acid alkyl ester monomer (A3) is preferably from 0.02 to 0.12, and more preferably from 0.04 to 0.12, from the perspective of achieving superior effect of the present technology and excellent storage stability (also referred to as “stability”; the same applies hereinafter).
• the molar ratio (A2/A3) of the (meth)acrylic silane coupling agent (A2) to the (meth)acrylic acid alkyl ester monomer (A3) is preferably from 0.01 to 0.07, and more preferably from 0.014 to 0.07, from the perspective of achieving superior effect of the present technology and excellent stability.
• the molar ratio (A4/A3) of the (meth)acrylic acid monomer (A4) to the (meth)acrylic acid alkyl ester monomer (A3) is preferably from 0.05 to 0.2, and more preferably from 0.1 to 0.2, from the perspective of achieving superior effect of the present technology and excellent stability.
• the molar ratio (A5/A3) of the hydroxy group-containing polymerizable monomer (A5) to the (meth)acrylic acid alkyl ester monomer (A3) is preferably from 0.08 to 0.18, and more preferably from 0.08 to 0.15.
• the content of the epoxy group-containing polymerizable monomer (A1) is preferably from 1 to 10 mol %, and more preferably from 2 to 9 mol % relative to the total number of moles of the epoxy group-containing polymerizable monomer (A1), the (meth)acrylic silane coupling agent (A2), the (meth)acrylic acid alkyl ester monomer (A3), the (meth)acrylic acid monomer (A4), and the hydroxy group-containing polymerizable monomer (A5).
• the total content of the epoxy group-containing polymerizable monomer (A1) and the (meth)acrylic silane coupling agent (A2) is preferably from 1.5. to 10.5 mol %, and more preferably from 1.5 to 10 mol % relative to the total number of moles of the epoxy group-containing polymerizable monomer (A1), the (meth)acrylic silane coupling agent (A2), the (meth)acrylic acid alkyl ester monomer (A3), the (meth)acrylic acid monomer (A4), and the hydroxy group-containing polymerizable monomer (A5).
• polymerizable monomer (A) is the second monomer composition.
• Phosphoric acid group-containing polymerizable monomer (AP) is described below.
• the phosphoric acid group-containing polymerizable monomer (AP) as the polymerizable monomer (A) is a compound having a (meth)acryloyl group and a phosphoric acid group.
• the (meth)acryloyl group and the phosphoric acid group can be bonded through an organic group.
• the organic group is synonymous with that described above.
• Examples of the phosphoric acid group-containing polymerizable monomer (AP) include a compound represented by Formula (1) below.
• R 11 is a hydrogen atom or a methyl group
• R 12 is a hydrocarbon group that may have a heteroatom
• m is 1 or 2
• n is from 1 to 9.
• the hydrocarbon group that may have a heteroatom is synonymous with that described above (the same applies hereinafter).
• the hydrocarbon group that may have a heteroatom is preferably an alkylene group.
• Examples of the alkylene group include an ethylene group, a trimethylene group, and a propylene group.
• m is preferably 2.
• n may be 1 or 2 to 9.
• phosphoric acid-containing polymerizable monomer examples include
• acid phosphoxy ethylmono(meth)acrylate and acid phosphoxy polyoxypropylene glycol mono(meth)acrylate are preferable from the perspectives of superior effect of the present technology and excellent adhesion and stability.
• the (meth)acrylic acid alkyl ester monomer (A6) as the polymerizable monomer (A) may be any alkyl ester of (meth)acrylic acid.
• the (meth)acrylic acid alkyl ester monomer (A6) is synonymous with the (meth)acrylic acid alkyl ester monomer (A3) described above.
• Examples of the (meth)acrylic acid monomer (A7) as the polymerizable monomer (A) include (meth)acrylic acid.
• the hydroxy group-containing polymerizable monomer (A8) as the polymerizable monomer (A) may be any compound having a (meth)acryloyl group and a hydroxy group.
• the hydroxy group-containing polymerizable monomer (A8) is synonymous with the hydroxy group-containing polymerizable monomer (A5) described above.
• (A6) is preferably 0.04 or less, and more preferably from 0.001 to 0.04, from the perspective of achieving superior effect of the present technology and excellent adhesion.
• the molar ratio (A7/A6) of the (meth)acrylic acid monomer (A7) to the (meth)acrylic acid alkyl ester monomer (A6) is preferably from 0.05 to 0.20, and more preferably from 0.05 to 0.15, from the perspective of achieving superior effect of the present technology and excellent adhesion and stability.
• the molar ratio (A8/A6) of the hydroxy group-containing polymerizable monomer (A8) to the (meth)acrylic acid alkyl ester monomer (A6) is preferably from 0.01 to 0.20, and more preferably from 0.05 to 0.10, from the perspective of achieving superior effect of the present technology and excellent adhesion.
• the (meth)acrylic acid alkyl ester monomer (A6), the (meth)acrylic acid monomer (A7), and the hydroxy group-containing polymerizable monomer (A8) is preferably from 0.1 to 3 mol %, and more preferably from 0.5 to 2.5 mol % from the perspective of achieving superior effect of the present technology and excellent adhesion and stability, the content of the phosphoric acid group-containing polymerizable monomer (AP) relative to the total number of moles of the phosphoric acid group-containing polymerizable monomer (AP).
• the production method of (meth)acrylic emulsion is not limited. Examples thereof include a method in which a polymerizable monomer (A) is polymerized in the presence of a polymerization initiator in a dispersion medium such as water to obtain a (meth)acrylic emulsion in which (meth)acrylic particles are dispersed as a dispersoid.
• the polymerization initiator used in the production method may be any compound that can subject a monomer having a vinyl-based functional group, such as a (meth)acryloyl group, to radical polymerization.
• a monomer having a vinyl-based functional group such as a (meth)acryloyl group
• radical polymerization examples thereof include azo compounds, such as 2,2′-azobisbutyronitrile (AIBN); and peroxides such as benzoyl peroxide (BPO).
• the polymerization initiator can be used alone or in combination of two or more types thereof.
• the used amount of the polymerization initiator is preferably from 0.002 to 1 mol % relative to the total number of moles of all the monomers (A1) to (A5) or the total number of moles of all of the monomer (AP) and monomers (A6) to (A8).
• the dispersion medium used in the production method is synonymous with that described above.
• the used amount of the dispersion medium may be from 60 to 700 parts by mass per 100 parts by mass of the polymerizable monomer (A).
• the reaction temperature in the production method may be from 60 to 80° C.
• the polymerization can be performed with agitation.
• a neutralizer may be further used.
• Any neutralizer that can neutralize an acidic group such as a carboxy group and a phosphoric acid group may be used.
• Examples thereof include sodium hydroxide, potassium hydroxide; ammonia water; and tertiary amines (B) described below.
• the neutralizer is preferably used in an amount such that, for example, the pH value of the emulsion after the neutralization becomes from approximately 7 to 10.
• vinyl monomers except the polymerizable monomer (A); reducing agents and chain transfer agents may be further used.
• the tertiary amine (B) contained in the composition of an embodiment of the present technology may be any compound in which three hydrocarbon groups that may have a heteroatom are bonded to a nitrogen atom.
• the tertiary amine (B) may form a salt (e.g. a carboxylate, a phosphate) by reacting with at least one type selected from the group consisting of a carboxy group and a phosphoric acid group contained in the (meth)acrylic particle.
• a salt e.g. a carboxylate, a phosphate
• the polymerizable monomer (A) is the second monomer composition and the tertiary amine (B) forms a salt by reacting with the carboxy group and the phosphoric acid group, superior effect of the present technology is achieved and excellent adhesion is achieved because the particle size of the (meth)acrylic particle becomes smaller.
• the tertiary amine (B) can produce a hydroxy group by reacting with an epoxy group contained in the (meth)acrylic particle.
• the hydrocarbon group that may have a heteroatom is not limited. Examples thereof include the groups listed above. Specific examples thereof include an aliphatic hydrocarbon group that may have a hydroxy group.
• tertiary amine (B) examples include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, and triethanolamine.
• the tertiary amine (B) can be used alone or in combination of two or more types thereof.
• the content of the tertiary amine (B) is preferably an amount by which the molar ratio (B/A4) of the tertiary amine (B) to the (meth)acrylic acid monomer (A4) used in the production of the (meth)acrylic emulsion becomes from 0.2 to 1.0, and more preferably from 0.3 to 1.0 from the perspective of achieving superior effect of the present technology and excellent stability.
• the content of the tertiary amine (B) is preferably an amount by which the molar ratio (B/A7) of the tertiary amine (B) to the (meth)acrylic acid monomer (A7) used in the production of the (meth)acrylic emulsion becomes from 0.1 to 1.0, and more preferably from 0.3 to 1.0 from the perspective of achieving superior effect of the present technology and excellent adhesion and stability.
• composition according to an embodiment of the present technology may further contain additives as necessary in a range that does not inhibit the object and effect of the present technology.
• additives include emulsions except the predetermined (meth)acrylic emulsion; amines except the tertiary amine; fillers, pigments, antiblocking agents, dispersion stabilizers, thixotropic agents, viscosity modifiers, leveling agents, antigelling agents, photostabilizers, anti-aging agents, antioxidants, UV absorbents, plasticizers, lubricants, antistatic agents, reinforcing materials, flame retardants, catalysts, antifoaming agents, thickeners, dispersants, and organic solvents.
• the type and the used amount of the additives may be selected as desired.
• the production method of the composition of an embodiment of the present technology is not limited.
• composition of an embodiment of the present technology can be produced by mixing the (meth)acrylic emulsion, the tertiary amine (B), and additives that may be used as necessary.
• composition of an embodiment of the present technology may be produced by using the tertiary amine (B) during the production of (meth)acrylic emulsion.
• the obtained (meth)acrylic emulsion can be used as is as a composition of an embodiment of the present technology.
• the composition of an embodiment of the present technology can be produced by further mixing the additives that may be used as necessary to the obtained (meth)acrylic emulsion.
• composition of an embodiment of the present technology can be used as a primer composition for a sealant.
• adherend to which the composition of an embodiment of the present technology can be applied examples include glass; metals such as aluminum, anodized aluminum, iron, galvanized steel plates, copper, and stainless steel; inorganic hard materials (foundation) such as mortar and stone materials; porous members such as mortar; coated members that are coated with fluoro electrodeposition, acrylic electrodeposition, fluorine coating, urethane coating, and acrylic urethane coating; cured products (e.g.
• sealants such as silicone-based, modified silicone-based, urethane-based, polysulfide-based, and polyisobutylene-based sealants; vinyl chloride resins, acrylic resins; rubbers such as acrylonitrile butadiene rubber (NBR) and ethylene-propylene-diene rubber (EPDM); and the like.
• NBR acrylonitrile butadiene rubber
• EPDM ethylene-propylene-diene rubber
• the method of using the composition of an embodiment of the present technology is exemplified by a method including: applying the composition of an embodiment of the present technology onto the adherend described above; optionally drying the composition; applying a sealant composition thereto; and then curing the composition of an embodiment of the present technology and the sealant composition.
• the temperature at which the composition of an embodiment of the present technology is dried is preferably 20° C. or higher from the perspective of achieving superior effect of the present technology and excellent adhesion and workability.
• the used sealant is not limited. Examples thereof include sealants for construction and automobiles. Specific examples thereof include silicone-based sealant, modified silicone-based sealant, polyurethane-based sealant, polysulfide-based sealant, and polyisobutylene-based sealant. Among these, polyurethane-based sealant, and especially polyurethane-based sealant for construction (urethane waterproof material) can be preferably used.
• the solid content is the total amount (mass %) of the monomer used in the production of the (meth)acrylic emulsion relative to the total amount of the water-based primer composition.
• Each of the water-based primer compositions was applied on mortar which was an adherend (50 mm length ⁇ 50 mm width; available from Paltek Corporation) by using a brush in a manner that the film thickness was 50 g/m 2 and dried at 25° C. for 3 hours to form a primer layer.
• a urethane waterproof material (trade name: HAMATITE URBAN ROOF U-8000, available from The Yokohama Rubber Co., Ltd.; urethane waterproof material) was poured onto the primer layer in a manner that the thickness was 5 mm, and the urethan waterproof material was cured in a condition at 25° C. and a relative humidity of 45% for 3 days to obtain an initial test piece.
• the separation test in a normal state was performed by holding an edge of the urethane waterproof material of the initial test piece obtained as described above by a hand and peeling off the urethane waterproof material from the initial test piece at an angle of 180° in a condition at 23° C.
• the results of the separation test in a normal state were evaluated based on the following evaluation criteria.
• the failure form of the adhesion interface after the separation test in a normal state was partial interfacial failure (20% or less relative to the total broken area) and cohesive failure of the primer, the case was evaluated as exhibiting poor adhesion and indicated as “B”.
• the failure state described above is referred to as “CF80 or greater but less than 100”.
• An initial test piece produced in the same manner as described above was immersed in water at 25° C. for a week, and then the test piece was taken out from the water, and this was used as a test piece for water resistance evaluation.
• the water resistant separation test was performed by holding an edge of the urethane waterproof material of the test piece for water resistance evaluation obtained as described above by a hand and peeling off the urethane waterproof material from the test piece for water resistance evaluation at an angle of 180° in a condition at 23° C. The results of the water resistant separation test were evaluated based on the following evaluation criteria.
• the water-based primer composition produced as described above was stored in a condition at 50° C. and a relative humidity of 45% for 5 days.
• the water-based primer composition after the storage was visually observed.
• test piece was prepared by the same procedure as the preparation of the initial test piece described above except for using the water-based primer composition after the storage, and the obtained test piece was used as the test piece for stability test evaluation.
• the separation test was performed by holding an edge of the urethane waterproof material of the test piece for stability test evaluation obtained as described above by a hand and peeling off the urethane waterproof material from the test piece for stability test evaluation at an angle of 180° in a condition at 23° C. The results of the separation test were evaluated based on the following evaluation criteria.
• Monomer (A1-1) glycidyl methacrylate (GMA, having the following structure), available from Tokyo Chemical Industry Co., Ltd.
• Monomer (A1-1) corresponds to an epoxy group-containing polymerizable monomer (A1).
• Monomer (A2-1) ⁇ -methacryloxypropyl methyldiethoxysilane (having the following structure), KBE-502, available from Shin-Etsu Chemical Co., Ltd.
• Monomer (A2-1) corresponds to a (meth)acrylic silane coupling agent (A2).
• Monomer (A3-1) methyl methacrylate (MMA).
• Monomer (A3-1) corresponds to a (meth)acrylic acid alkyl ester monomer (A3).
• Monomer (A3-2) 2-ethylhexyl acrylate (2EHA).
• Monomer (A3-2) corresponds to a (meth)acrylic acid alkyl ester monomer (A3).
• Monomer (A4-1) methacrylic acid (MAA).
• Monomer (A4-1) corresponds to a (meth)acrylic acid monomer (A4).
• Monomer (A5-1) 2-hydroxyethyl methacrylate (HEMA).
• Monomer (A5-1) corresponds to a hydroxy group-containing polymerizable monomer (A5).
• Polymerization initiator 2,2′-azobisisobutyronitrile (AIBN).
• Comparative Example 1 in which the polymerizable monomer (A) contained no epoxy group-containing polymerizable monomer (A1), exhibited poor water resistance.
• compositions of embodiments of the present technology exhibited a predetermined effect.
• Example 2 When Examples 2 and 3 are compared with Example 1, it was found that superior water resistance can be achieved when A2/A3 was greater than 0.02.
• Example 3 When Examples 1 and 2 are compared with Example 3, it was found that excellent stability can be achieved when A2/A3 was less than 0.08.
• Example 4 When Example 4 and Examples 1 and 5 are compared, it was found that excellent stability can be achieved when A1/A3 was less than 0.060.
• Monomer (A6-1) methyl methacrylate (MMA).
• Monomer (A6-1) corresponds to a (meth)acrylic acid alkyl ester monomer (A6).
• Monomer (A6-2) 2-ethylhexyl acrylate (2EHA).
• Monomer (A6-2) corresponds to a (meth)acrylic acid alkyl ester monomer (A6).
• Monomer (A7-1) methacrylic acid (MAA).
• Monomer (A7-1) corresponds to a (meth)acrylic acid monomer (A7).
• Monomer (A8-1) 2-hydroxyethyl methacrylate (HEMA).
• Monomer (A8-1) corresponds to a hydroxy group-containing polymerizable monomer (A8).
• Monomer (AP-1) acid phosphoxy polyoxypropylene glycol mono(meth)acrylate (having the following structure), available from Uni Chemical K.K.
• Monomer (AP-1) corresponds to a phosphoric acid group-containing polymerizable monomer (AP).
• Monomer (AP-2) 2-methacryloyloxyethyl acid phosphate (having the following structure), available from Kyoeisha Chemical Co., Ltd.
• Monomer (AP-2) corresponds to a phosphoric acid group-containing polymerizable monomer (AP).
• Comparative Example 1 in which the polymerizable monomer (A) contained no phosphoric acid group-containing polymerizable monomer (AP), exhibited poor adhesion and water resistance.
• compositions of embodiments of the present technology exhibited a predetermined effect. Furthermore, the compositions of embodiments of the present technology exhibited excellent adhesion.
• Example 2 When Examples 2 to 4 are compared with Example 1, it was found that superior water resistance can be achieved when AP/A6 was 0.01 or greater.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Dispersion Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Sealing Material Composition (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (5)

Publications (1)

Family

ID=58517205

Family Applications (1)

Country Status (3)

Cited By (2)

Families Citing this family (2)

Citations (2)

Family Cites Families (12)

• 2016
  • 2016-10-12 CN CN201680059419.1A patent/CN108137982B/zh active Active
  • 2016-10-12 US US15/768,503 patent/US20180312699A1/en not_active Abandoned
  • 2016-10-12 WO PCT/JP2016/080253 patent/WO2017065174A1/ja active Application Filing

Patent Citations (2)

Also Published As

Similar Documents

Legal Events